Cyano-and cyanomethyl-benzensulfonamides

ABSTRACT

Certain substituted cyanobenzenesulfonamides, nitrobenzenesulfonamides, trifluoromethylbenzenesulfonamides, halobenzenesulfonamides, and cyanomethylbenzenesulfonamides are effective preemergence and postemergence herbicides, which may be used for selective weed control in certain crops.

O United States Patent [1 1 [111 3,888,897 Martin June 10, 1975 CYANO-AND [56] References Cited CYANOMETHYL-BENZENSULFONAMIDES U D S E PATENTS [75] Inventor: Elmore Louis Martin, Wilmington, 3,518,075 6/1970 Brokke et al. 71/103 OTHER PUBLICATIONS [731 Assigneei Pom de Nemours and Nowell: Chemical Abstracts, Vol. 7, p. 1166.

Company, Wilmington, Del.

[22] Filed; Feb. 21, 1973 Primary ExaminerLewis Gotts pp No: 334,411 Assistant ExaminerDolph H. Torrence Related US. Application Data [57] ABSTRACT Continuation-impart 0f 243,404, April Certain substituted cyanobenzenesulfonamides, ni- 972, abandonedtrobenzenesulfonamides, trifluoromethylbenzenesulfonamides, halobenzenesulfonamides, and cyanometh- [52] 260/465 E; 260/556 AR; 260/556 B; ylbenzenesulfonamides are effective preemergence 71/103 and postemergence herbicides, which may be used for [51] Int. Cl. C07c 121/52 selective weed comm] in certain crops [58] Field of Search 260/465 E; 71/103 3 Claims, N0 Drawings CYANO-AND CYANOMETHYL-BENZENSULFONAMIDES CROSS REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of my copending application Ser. No. 243,404, filed Apr. 12, 1972, now abandoned.

BACKGROUND OF THE INVENTION SUMMARY OF THE INVENTION Certain cyanobenzenesulfonamides, halobenzenesulfonamides, nitrobenzenesulfonamides, trifluoromethylbenzenesulfonamides, and cyanomethylbenzenesulfonamides exhibit selective herbicidal activity and can be used in the presence of valuable crops, e.g., soybeans, wheat, corn, rice, peanuts, and cotton. These compounds are represented by Formula (1).

SO2NR5R6 wherein Z is cyano, halogen, cyanomethyl, nitro or trifluoromethyl;

R R R and R are the same or different and are independently selected from the group consisting of hydrogen, alkyl of 2 to 7 carbon atoms and halogen provided that: a. two of R R R and R are alkyl of 2 to 7 carbon atoms; I no alkyl groups are ortho to each other; c. at least one of R R R and R is alkyl of 3 to 7 carbon atoms; d. two of R,, R R and R are independently hydrogen or halogen; e. the total carbon content of R R R and R is not greater than 9 carbon atoms; and f. each alkyl group has from 2 to 3 carbon atoms in a straight chain from the point of attachment to the aromatic ring; and g. when Z is nitro, both R and R must be alkyl groups. R is hydrogen, alkyl of 1 to 3 carbon atoms, allyl or propynyl; R is hydrogen, alkyl of 1 to 3 carbon atoms, allyl, propynyl, lithium, sodium, potassium, calcium or 2 acyl of l to 3 carbon atoms; and R to R together can form where m is O or 1 and n is O or 1.

Preferred because of higher herbicidal activity are those compounds of Formula (1) where each of R R and R is hydrogen; R is hydrogen, lithium, sodium or potassium; R and R are each independently alkyl of 3 to 5 carbon atoms; and Z is cyanao, rine. Most preferred because of its safety to cotton and peanuts is 4-cyano-2,5-diisopropylbenzenesulfonamide and because of its safety to rice is 4-chloro-2,5- diisopropylbenzenesulfonamide.

The halobenzenesulfonamide compounds are intermediates in the synthesis of the above cyanobenzenesulfonamides which in turn can be used to prepare the cyanomethylbenzenesulfonamides and trifluoromethylbenzenesulfonamides in those cases where shorter routes are not applicable.

DETAILED DESCRIPTION OF THE INVENTION Compounds of Formula l can be prepared by many processes based on methods generally well-known in the art. The starting materials for these compounds are alkylbenzenes. Many of these are commercially available. Those not available are easily synthesized by wellknown methods. Simple cyanobenzenesulfonamides can be made, for instance, by bromination of the corresponding dialkylbenzenes, chlorosulfonation of the resulting bromodialkylbenzenes, amidation of the resulting bromodialkylbenzenesulfonyl chlorides with ammonia or an alkylor dialkylamine, and replacement of the bromo group with a cyano group. This reaction is illustrated by the following equations. The illustration shows reactions beginning with 1,4-diisopropylbenzene. Other appropriately substituted alkylbenzenes can be substituted for this compound Halogenated cyanobenzenesulfonamides can be prepared is a similar manner as shown below.

bromine or chlo-- Alternatively:

Cyanomethylbenzenesulfonamides can be prepared from cyanobenzenesulfonamides by well-known methods for the conversion of a cyano group to a cyanomethyl group. This conversion is illustrated by the following equations:

/ I 502N112 0 c m aocn ca on, N 1) OH 2 2 H06 Nitrobenzenesulfonamides can be prepared as fol- 2) so /cuc1 Trifluoromethylbenzenesulfonamides can be prepared from cyanobenzenesulfonamides as follows.

QO NH 1) OH /HOCH CH OH O N'H Continued Compounds where Z is cyano are most active. When Z is halogen, chlorine and bromine are preferred. Compounds where Z is CN, C] or Br combine ease of manufacture and good activity.

Of the substituents R to R it is preferred for obtaining high activity that R and R are alkyl of 3-5 carbon atoms and R and R are hydrogen. It is most preferred that R and R are isopropyl.

It is preferred that R is hydrogen and that R is hydrogen, lithium, sodium or potassium.

Most preferred because of its safety to cotton and peanuts is 4-cyano-2,5-diisopropylbenzenesulfonamide and because of its safety to rice is 4-chloro-2,5- diisopropylbenzenesulfonamide.

The compounds of this invention are useful for general weed control or as selective herbicides. Preemergence surface applications are most useful but preplant incorporated or postemergence treatments are sometimes preferred. They provide control of many beans, wheat, rice, corn, sugarcane and cotton. Gen- 60 eral weed control on industrial sites and the like is provided by rates of 5 to 30 kg/ha. The compounds are most advantageously applied preemergence to crops at rates of 0. 1 2 to 4 k g/ha, depending on the specific crop, the weed to be controlled, the soil and environmental conditions and the particular chemical used. Under certain conditions, such as lack of rainfall for an extended period after application, it is advantageous to lightly incorporate these compounds into the soil. Selected members of this class of compounds have postemergence activity and may be used at rates of 1 to kg/ha for postemergence weed control, if applied while susceptible weeds are young, preferably in the two-leaf stage of development. Two or more compounds of this It is sometimes advantageous to combine a compound of this invention with another herbicide in order to broaden the spectrum of weeds controlled or to increase the residual effect on industrial sites or to minimize the chances of injury to the current or subsequent crops. The exact combination which may be used to the best advantage will depend upon the weeds to be controlled, the environmental conditions or, in agricultural work, the crop being produced. The proper combinal,4-diisopropylbenzene in 320 parts of carbon tetrachloride, there is added over 15 min. 154 parts of chlorosulfonic acid. After stirring. 30 min. longer, the reaction mixture is poured onto 1000 parts of ice. The organic layer is separated and Washed with 200 parts of water and then dried over magnesium sulfate. Removal of the solvent under reduced pressure gives 105 parts of 4-bromo-2,5-diisopropylbenzenesulfonyl chloride which can be recrystallized from n-hexane, m.p. 80-83.

1,4-Diisopropyl-2-iodobenzene can be prepared by the method of H. Suzuki et al., Bull. Chem. Soc. (Japan) 39, 128 (1966); Org. Syn., 51, 94 (1971). 2- Fluoro-1,4-diisopropylbenzene can be prepared by halogen interchange with the iodo compound by heating with a large excess of potassium fluoride in refluxing DMF for 6 hr.

Similarly dialkyldihalobenzenesulfonyl chlorides can be prepared by appropriate substitution in the above example.

EXAMPLE 2 3-Chloro-2,5-diisopropylbenzenesulfonyl chloride A .sealed autoclave, charged with 288 parts of 2,5- diisopropylbenzenesulfonyl; chloride, 5 parts of antimony pentachloride and 600 parts carbon tetrachloride and 36 parts chlorine, is shaken at 150 for 6 hr. The reaction solution is washed with sodium bisulfite and water. The washed solution is dried and the solvent distilled under reduced pressure. The crude residue can tion, however, can be readily selected by one with ordiother herbicides such as linuron (Lorox), atrazine (Aatrex), amiben (Amiben), 2,4-D (2,4-dichlorophenoxyacetic acid), molinate (Ordram),.propanil (Stam or Rogue) and 3-(p-cumenyl)-1,l,-dimethylurea. Combinations of this type will broaden the spectrum of weeds controlled and reduce the rate of each herbicide used, thus reducing the chances of crop injury and persistence of the chemicalslonger than necessary to provide weed control. I

The preparation of representative halobenzenesulfonamides, cyanobenzenesulfonamides, nitrobenzenesulfonamides, trifluoromethylbenzenesulfonamides and cyanomethylbenzenesulfonamides is illustrated in the following examples, wherein all parts, proportions, and percentages are by weight and all temperatures are in degrees Centigrade unless indicated otherwise.

EXAMPLE 1 4-Bromo-2,5-diisopropylbenzenesulfonyl Chloride To a one-liter flask containing 80 parts of 2-bromobe recrystallized from a suitable solvent to give 3-,

chloro-2,5-diisopropylbenzenesulfonyl chloride.

Similarly dialkyldihaloand dialkyltrihalobenzenesulfonyl chlorides can be prepared from dialkylhaloand dialkyldihalobenzenesulfonyl chlorides by appropriate substitution in the above procedure. Where isomeric mixtures are obtained, the isomers can be separated by chromatography or fractional crystallization.

EXAMPLE 3 I 4-Bromo- 2,5-diisopropylbenzenesulfonamide To a one-liter flask containing parts of concentrated aqueous ammonia and parts of ether, there is added over three hours, 105 parts of 4-bromo-2,5-

vdiisopropylbenzenesulfonyl chloride in parts of ether. After stirring two hours longer, the excess ammonia is neutralized by adding 10% HCl. The organic layer is washed two times with 200 parts of saturated sodiumchloride and is dried over sodium sulfate. Re-- moval of the solvent gives 92 parts of 4-bromo-2,5- diisopropylbenzenesulfonamide which may be recrystallized from l-chlorobutane, m.p. l.45152.

N-Alkyland N,N-dialkylbenzenesulfonamides can be prepared by replacement of ammonia with alkylor dialkylamines in the above example.

The following dialkylhalobenzenesulfonamides, dialkyldihalobenzenesulfonamides, and dialkyltrihalobenzenesulfonamides can be prepared from the listed dialkylbenzenes, dialkylhalobenzenes and dialkyldihalobenzenes by the methods described in the above examples. Where isomeric mixtures are formed, the isomers are separated by chromatograpahy or fractional crystallization.

EXAMPLE 4 4-Cyano-2,5-diisopropylbenzenesulfonamide,

A one-liter flask containing 92 parts of 4-bromo-2,5- diisopropylbenzenesulfonamide, 30 parts of cuprous cyanide, and 250 parts N-methylpyrrolidone is heated at 190-200 for 2 hours. The reaction mixture is cooled to 100 and is poured into 1000 parts water. The precipitated material is filtered. It is heated for 2 hours near reflux with 1000 parts water and 30 parts sodium cyanide. The reaction is cooled and the precipitate filtered to obtain 60 parts 4-cyano-2,5-diisopropylbenzenesulfonamide. The solid can be recrystallized from methanol, and then exhibits a rn.p. of 200-202.

EXAMPLE 5 5-Bromo-2-cyano-3,6-diisopropylbenzenesulfonamide and 5-cyano-2-bromo-3,6-diisopropylbenzenesulfonamide A one-liter flask containing 38 parts 2,5-dibromo- 3,6-diisopropy]benzenesulfonamide, 9 parts of cuprous cyanide, and 125 parts N-methylpyrrolidone is heated at 200 for 2 hrs. The reaction mixture is cooled to 100 and is then poured into 500 parts water. The precipitated material is filtered and then is heated for 2 hrs. near reflux with 500 parts water and parts sodium cyanide. The reaction is cooled and the precipitate filtered to obtain a mixture of 5-bromo-2-cyano-3,6- diisopropylbenzenesulfonamide and 5-cyano-2-bromo- 3,6-diisopropylbenzenesulfonamide. The mixture is separated by chromatography, and then the individual compounds are purified by recrystallization.

By appropriate substitution the following cyanodialkylbenzenesulfonamides, cyanodialkylhalobenzenesulfonamides, and cyanodialkylhalobenzenesulfonamides can be prepared.

TABLE 2 4-Cyano-2,5-di-n-propylbenzenesulfonamide, m.p. l04-106.5 4-Cyano-2,5-di-sec-butylbenzenesulfonamide, b.p.

190 (0.06 mm) 4-Cyano-2,5-di-sec-butyl-N,N-dimethylbenzenesulfonamide 2-sec-Butyl-4-cyano-5-isopropylbenzenesulfonamide, b.p. 198 (0.15 mm) 2-sec-Butyl-4-cyano-5-isopropy1-N methylbenzenesulfonamide, m.p. 160l63 4-cyano-5-ethyl-2-isopropyl-N-ethylbenzenesulfonamide 2-sec-Butyl-4-cyano-5-n-propyl-N-ally1benzenesulfonamide 4-cyano-2 ,5-diisopropyl-N,N-dipropylbenzenesulfona 5-tert-Butyl-3-cyano-2-ethylbenzenesulfonamide 5-tert-Butyl-3-cyano-2-isopropylbenzenesulfonamide 5-tert-Butyl-2-isobutyl-3-cyano-N,N-dimethylbenzenesulfonamide 4-Cyano-N,N-diallyl-2,5- mide b.p. 147 (0.07 mm) 4-Cyano-N,N-diethyl-2,5-diisopropylbenzenesulfonamide, m.p. 9194 4-Cyano-2,5-diisopropyl-N,N-dimethylbenzenesulfonamide, m.p. 138l44 4-Cyano-5-ethyl-2-( 1 l ,2,2-tetramethylpropyl)benzenesulfonamide 5-tert-Butyl-2-sec-butyl-3-cyanobenzenesulfonamide 3-Cyano-5-isopropy.-2-n-propy1-N-ethylbenzenesule fonamide 3-Cyano-5-(1,1-dimethylpropyl)-2-isopropylbenzenesulfonamide 3-Cyano-2,5-di-sec-butylbenzenesulfonamide 5-sec-Buty1-3-cyano-2-n-propylbenzenesulfonamide 3-Cyano-2-ethy1-5-( 1 ,2,2-trimethylpropyl)benzenesulfonamide 4-Cyano-1 ,3-diisobutylbenzenesulfonamide 4-Cyano-1,3-diisopropyl-N-methylbenzenesulfonamide 4-Cyano-1 ,3-diisopropyl-N,N-dimethylbenzenesulfonamide 5-Cyano-2,4-diisopropylbenzenesulfonamide 3-Cyano-2,4-diisopropy1benzenesulfonamide 4-Cyan0-5-isobuty1-2-isopropylbenzenesulfonamide, m.p. l11ll4 4-Cyano-2,6-diisopropylbenzenesulfonamide 2-Bromo-5-Cyano-3,6-diisopropylbenzenesulfonamide 2-Bromo-4-cyano-3,6-diisopropylbenzenesulfonamide 3-Bromo-5-cyano-2,6-diisopropylbenzenesulfonamide diisopropylbenzenesulfona- 3-Bromo-5-cyano-2,4-diisopropylbenzenesulfonamide 5-Bromo-3 -cyano-2 ,4-diisopropylbenzenesulfonamide 3-Cyano-2 ,5-diisopropylbenzenesulfonamide 3-Cyano-2 ,6-diisopropylbenzenesulfonamide 4-Cyano-3 ,6-dibromo-2,5 -diisopropylbenzenesulfonamide 1 3-Bromo-6 chloro-4-cyano-2 ,5-diisopropylbenzenesulfonamide 6-Bromo-3 -chloro-4-cyano-2,S-diisopropylbenzenesulonamide 3-Bromo-4-cyano-2,5-diisopropylbenzenesulfonamide 3-Chloro-4-cyano-2,5-diisopropylbenzenesulfonamide I EXAMPLE 6 2,-Diisopropylbenzenesulfonyl Chloride One equivalent part by weight of 2,6-

diisopropylaniline is diazotized with 1.1 equivalent 1 1 12 parts of sodium nitrite and 1.1 equivalent parts of hy- Table 4-Continued drochloric acid in acetic acid at to This solution is added dropwise with stirring to a solution of acetic Starting Material Product acid containing 1 equivalent part of cuprous chloride and excess sulfur dioxide at When the addition is 5 -Ethyl-5-isopropyl-4- 2-Ethyl-5-isopropyl-4- nitroaniline nitrobenzenesulfonamide complete and nitrogen evolution ceases, the mixture is poured into ice water and the oily product extracted into ether. The organic layer is washed with water and dried over sodium sulfate. Removal of the solvent gives EXAMPLE 7 2,6-diisopropylbenzenesulfonyl chloride which may be 10 purified by distillation.

By appropriate substitution in the above procedure,

the following benzenesulfonyl chlorides are made.

3 ,4-Dibromo-2,5-diisopropylbenzenesulfonamide 3-Amino-4-bromo-2,5-diisopropylbenzenesulfona mide is prepared by known general methods (L.F. Fuser and M. Fieser, Reinhold Publishing Corp., N.Y.,

TABLE 3 3rd ed., 1956, pgs 599-602) from 2,5-

diisopropylamiline by acylation to 2,5-

Stafiing Material Pmduct diisopropylacetanilide, bromination to 4-bromo-2,5- 4-Bromo-2,5-diisopropyl-3- 4-Bromo-2,5-diisopropyl-3- dfisopropylacgianilid? bydrolysls to P nitroaniline nitrobenzenesulfonyl Chloride dnsopropylanilme, nltratlon t0 4-bromo-2,5-dnsopro- 4 Bromo 2yidfisobutyby 4 Bmmo 2,5 diisobutyl 3 pyl-3-n1troar1il1ne, diazotization 1n the presence of cunitroaniline nitrobenzenesulfonyl Chloride p s chloride and sulfur dloxlde to diisopropyl-3-nitrobenzenesulfonamide (method of Example 6) and reduction.

U i the p ocedure of Example 6 for preparing sul 3-Amino-4-bromo-2,5-diisopropylbenzenesulfonafonyl chlorides from arilines followed by reaction of the id i di i d i h 1,1 equivalent parts f di sulfonyl chlorides with various amines or ammonia, the nitrite and 1.1 equivalent parts of hydrobromimc acid following 2,5-dialkyl-4-nitrobenzenesulfonamides are at 5 in acetic acid. The diazonium mixture is added prepared: portionwise to a flask containing 2 equivalent parts of cuprous bromide and hydrobromic acid in 25 parts of TABLE 4 3 water at reflux. When the nitrogen evolution ceases, Stamn Material Product the reaction mixture is cooled and the product which g solidifies is filtered and washed with water. The prod- 2,5-DiiSOPr0Py1-4-nitr0afliline P Py uct may be further purified by recrystallization from nitrobenzenesulfonamlde, mp. ethanol water l90-l94(d) I n 5 If hydrochloric acid 1s substituted for hydrobromic 2,5-Diisopropyl-4-nitr0aniline 2,5-Dusopropyl-N,N-dimethyl-4- acid and cuprous cyanide for cuprous bromide the nitrobenzenesulfonamlde, m.p. i 148-151" am1no-4-bromo-2 ,5 -dnsopropylbenzenesulfonamide ma be converted to 4-bromo-3-c ano 2,5-diiso r0 1- 2,5-Diisopropyl-4-nitroaniline N,N-Diallyl-2,5-dnsopropyl-4- b y If d y p py nitrobenzenesulfonamide enZel'leSU onami e. g 2 l5 1 l 2 th 1 2] I 5 l 2 By appropriate substitution in the above procedure,

-lsopropy- -trime ysopropypmWUAmitmaniline trimthylpmpyl) 4 the following cyano and halobenzenesulfonamides are nitrobenzenesulfonamide I made.

TABLE 5 Starting Material Product 3-Arflino-4,%dibromo-2,5-diisopropylbenzene- 3-Cyano-4,6-dibromo-2,5-diisopropylbenzenesulfonamide su onaml e v 3-Arniio-4,6-dibromo-2,S-diisobutylbenzenesulfon- 3-Cyano-4,6-dibromo-2,5-diisobutylbenzenesulfonamide ami e- 3-Amino-4-bromo-2,5-diisopropylbenzenesulfonamid 4-Bromo-3-cyano-2,S-diisopropylbenzenesulfonamide 3-Amino-4-bromo-2,5-diisobutylbenzenesulfonamide 4-Bromo-3-cyano-2,5-diisobutylbenzenesulfonamide 3-Am icrio-4,6-dibromo-2,S-diisopropylbenzenesulfon- 2,5-Diisopropyl-3,4,6-tribromobenzenesulfonamide aml e 3-Amino-4-bromo-6-chlore-2,5-diisopropylbenzene- 6-Chloro-3,4-dibromo-2,5-diisopropylbenzenesulfonamide sulfonamide 3-ATfin0-4,%dibromo-2,S-diisopropylbenzene- 3-Chloro-4,6-dibromo-2,S-diisopropylbenzenesulfonamide su onami e 3-Am i5|o-4,6-dibrom0-2,5-diisobutylbenzenesulfon- 2,5-Diisobutyl-3,4,6-tribromobenzenesulfonamide am e 3-Amino-4-bromo-6-chloro-2,S-diisobutylbenzene- 6-Chloro-3,4-dibromo-2,5-diisobutylbenzenesulfonamide sulfonamide 3-Am iio-4,6-dibromo-2,5-diisobutylbenzenesulfon- 3-Chloro-4,6-dibromo-2,5-diisopropylbenzenesulfonamide am e 3-Am i1o-4-bromo-2,5-diisopropylbenzenesulfon- 3,4-Dibr0mo-2,5-diisopropylbenzenesulfonamide ami e 3-Amiio-4-bromo-2.5-diisopropylbenzenesulfon- 4-Bromo-3-chloro-2,5-diisopropylbenzenesulfonamide am e 3-Am ino-4-bromo-2,5-diisobutylbenzenesulfon- 3,4-Dibromo-2,5-diisobutylbenzenesulfonamide am e 3-Am ino-4-bromo-2,5-diisobutylbenzenesulfon- 4-Bromo-3-chloro-2,5-diisobutylbenzenesulfonamide amide 13 EXAMPLE 8 Part A 4-Carboxy-2,5-diisopropylbenzenesulfonamide Twenty parts 4-cyano-2,5-diisopr0pylbenzenesulfonamide is refluxed with 50 parts of potassium hydroxide and 400 parts of ethylene glycol under nitrogen for 24 hours. The cooled reaction mixture is diluted with 600 parts of water and acidified with hydrochloric acid. The precipitated product is filtered and washed with water. Drying gives 17 parts of 4-carboxy-2,5- diisopropylbenzenesulfonamide having a m.p. of 225-231.

Part B 4-Hydroxymethyl-2,5-diisopropylbenzenesulfonamide 4-Carboxy-2,5-diisopropylbenzenesulfonamide, 60

parts in 250 parts of ether and 250 parts of tetrahydrofuran is added dropwise to 24 parts of lithium aluminum hydride in 500 parts of ether at a rate where the ether refluxes gently. The reactants are then refluxed for 16 hours. Dilute hydrochloric acid is then added dropwise until the inorganic salts precipitate. The mixture is filtered and dried over sodium sulfate. After filtration and solvent removal there remains 41 parts of 4-hydroxymethyl-2,5-diisopropylbenzenesulfonamide having a m.p. of 185189.

Part C 4-Bromomethyl-2,5-diisopropylbenzenesulfonamide To 26 parts 4-hydroxymethyl-2,S-diisopropylbenzenesulfonamide dissolved in 100 parts chloroform heated just beleow reflux is added hydrogen bromide in a slow stream for an hour. The organic phase is washed 7 with aqueous sodium bicarbonate, dried oer magnesium sulfate and concentrated in vacuo to give 4- bromomethyl-2,5-diisopropylbenzenesulfonamide.

Part D 4-Cyanomethyl-2,5-diisopropylbenzenesulfonamide To 32 parts 4 -bromomethyl-2,5-diisopropylbenzenesulfonamide in 100 parts dimethylsulfoxide is added 10 parts sodium cyanide. The reaction is heated at 6570 for 30 minutes and then poured into ice water to give 4-cyanomethyl.-2,5-diisopropylbenzenesulfonamide. Purification is accomplished by recrystallization or chromatography on Florisil, silica gel, alumina, etc., but the relatively pure reaction product is useful in the composition and methods of this invention without purification.

The following .cyanomethyldialkylbenzenesulfonamides, cyanomethylhalodialkylbenzenesulfonamides,

and cyanomethyldialkyl-N,N-dialkyl (or N-alkyl) ben- Table 6 4-Cyanomethyl-2,5-di-n-propylbenzenesulfonamide 2,5 -Di-sec-butyl-4cyanomethyl-N,N-dimethylbenzenesulfonamide l 4 2-sec-Butyl-4-cyanomethyl-5-isopropylbenzenesulfonamide 5-sec-Butyl 4-cyanomethyl-2-isopropyl-N-methylbenzenesulfonamide 4-Cyanomethy1-5-ethyl-2-isopropyl-N-ethylbenzenesulfonamide 2-sec-Butyl-4-cyanomethyl-5-n-propyl-N-allylbenzenesulfonamide 5-Isobutyl-4-cyanomethyl-2-( l ,2-dimethylpropyl)-N- n-propylbenzenesulfonamide 4-Cyanomethyl-5-isopropyl2-( 1 ,1 ,2-trimethylpropyl)- N,N-di-n-propylbenzenesulfonamide 4-Cyanomethyl-5-n-propyl-2-( 1,2,2-trimethylpropyl)- N,N-dimethylbenzenesulfonamide 2-sec-Butyl-5-cyanomethyl-4-isopropyl-N-propargylbenzenesulfonamide 4-sec-Butyl-5-cyanomethyl-2-isopropyl-N,N-diethylbenzenesulfonamide 4-Isobutyl-2-sec-butyl-5-cyanomethylbenzenesulfonamide 5-Cyanomethyl-2-( 1,2-dimethylpropyl)-4-ethyl-N,N- dimethylbenzenesulfonamide 5-Cyanomethyl-4-n-propyl-2-( 1,2,2-trimethylpropyl)- N-methylbenzenesulfonamide 5 -tert-Butyl-3-cyanomethyl-2-ethylbenzenesulfonamide 5-tert-Butyl-3-cyanomethyl-2-isopropylbenznesulfona-' mide 5-tert-Butyl-2-isobutyl-3-cyanomethyl-N,N-dimethylbenzenesulfonamide 5-tert-Butyl-Z-sec-butyl-3-cyanomethylbenzenesulfonamide 3 -Cyanomethyl-5-isorpopyl-2-n-propyl-N-ethylbenzenesulfonamide 3-Cyanomethyl-5-( 1 ,1-dimethylpropyl)-2-isopropylbenzenesulfonamide '3-Cyanomethyl-2,5-di-sec-butylbenzenesulfonamide 5-sec-Butyl-3-cyanomethyl-2-n-propylbenzenesulfonamide 3-Cyanomethyl-2-ethyl-2-ethyl-5-( 1,2,2- trimethylpropyl )benzenesulfonamide S-Cyanomethyl-l ,4-diisobutylbenzenesulfonamide S-Cyanomethyl-l ,4-diisopropyl-N-methylbenzenesulfonamide S-Cyanomethyl- 1 ,4-diisopropyl-N ,N-dimethylbenzenesulfonamide 1 5-Cyanomethyl-2,4-diisopropylbenzenesulfonamide 3-Cyanomethyl-2,4-diisopropylbenzenesulfonamide 4-QIanomethy1-3-isobutyl-5-isopropylbenzenesulfonamide 4-Cyanomethyl-2,6-diisopropylbenzenesulfonamide 2-Bromo-5-cyanomethyb3 ,6-diisopropylbenzenesulfonamide 2-Bromo-4-cyanomethyl-3,6-diisopropylbenzenesulfonamide 3-Bromo-5-cyanomethyl-2,6-diisopropylbenzenesulfonamide 3-Bromo-5-cyanomethyl-2,4-diisopropylbenzenesulfonamide 5-Bromo-3-cyanomethyl-2,4-diisopropylbenzenesulfonamide 3-Cyanomethyl-2,5-diisopropylbenzenesulfonamide 3-Cyanomethyl-2,6-diisopropylbenzenesulfonamide '3-Cyanomethyl-4,6-dibromo-2,5-diisopropylbenzenesulfonamide I 3-Bromo-6-chloro-4-cyanomethyl-2,5-diisopropylbenzenesulfonamide 1 5 6-Bromo-3-chloro-4-cyanomethyl-2,S-diisopropylbenzenesulfonamide 3-Cyanomethyl-4,6-dibromo-2,5-diisobutylbenzenesulfonamide 3-Bromo-6-chloro-4 zenesulfonamide 6-Bromo-3-chloro-4-cyanomethyl-2,5-diisobutylbenzenesulfonamide 4-Bromo-3-cyanomethyl-2,5-diisopropylbenzenesulfonamide -cyanomethyl2,5-diisobutylben- I 4-Bromo-3-cyanomethyl-2,5-diisobutylbenaenesulfonamide 3-Bromo-4-cyanomethyl-2,5-diisopropylbenzenesulfonamide 3-Chloro-4-cyanomethyl-2,5-diisopropylbenzenesulfonamide 3-Bromo-4-cyanomethyl-2,5-diisobutylbenzenesulfonamide 3-Chloro-4-cyanomethyl-2,5-diisobutylbenzenesulfonamide I 4-Cyanomethyl-3,6-dibromo-2,S-diisopropylbenzenesulfonamide 4-Cyanomethyl-3,6-dibromo-2,5-diisobutylbenzenesulfonamide EXAMPLE 9 5-tert-Butyl-2-ethyl-3-nitrobenzenesulfonyl Chloride 5-tert-Butyl-2-ethylbenzenesulfonyl chloride, 52

' parts is added over /a hour to 190 parts of fuming nitric acid and 25 parts of sulfuric acid at 0 to 10. The reactants are stirred 2 hours at 0 to 10 and then at 25 for 2 hours. The reaction mixture is then poured onto ice.

The product is extracted into methylene dichloride, which is washed with water and then dried over magnesium sulfate. Solvent removal gives 51 parts of the sulfonyl chloride which is pure enough to be used for the preparation of sulfonamides.

Using this procedure for preparing nitrobenzenesulfonyl chlorides, the corresponding nitrobenzenesulfonamides may be prepared using the procedures mentioned earlier for sulfonamide preparations from sulfonyl chlorides. In cases where a mixture of isomeric sulfonyl chlorides is obtained, the mixture is converted to a mixture of sulfonamides which can be used as the mixture or chromatographed on alumina or silica gel to give the isomerically pure sulfonamides.

Table 7 Starting Material Product 2,S-Diisobutylbenzenesulfonyl 2,5-Diisobutyl-3-nitrochloride bcnzenesulfonamide 2,5-Dipropylbenzenesulfonyl 3-Nitro-2,5-dipropylbenchloride 7 zenesulfonamide 2,5-Dipropylbenzenesulfonyl N,N-dialkyl-3-nitro-2,5- chloride dipropylbenzenesulfonamide EXAMPLE 10 Part A 2,5-Diis0propyl-4-trifluoromethylbenzenesulfonyl 1 Fluoride 4-Carboxy-2,5-diisopropylbenzenesulfonamide, 10

parts, sulfur tetrafluoride, 30 parts, and hydrogen fluo- A ride, 12 parts is heated in a l-lastelloy-lined bomb for 2 hours at 3 hours at and 5 hours at On cooling, the crude product is dissolved in methylene dichloride, treated with sodium fluoride and then filtered. Removal of the solvent gives 9.5 parts of 2,5- diisopropyl-4-trif1uoromethylbenzenesulfonyl fluoride which may be purified by vacuum sublimation,'and then exhibits a mLp. of l40'146.

Part B TABLE 8 Starting Material Product 7 2,5-Diisopropyl-N-propyl 4- 4-Cyano-2,5-diisopropylbentrifluoromethylbenzenesulfonamide zenesulfonamide 4-Cyano-2,5-d(ijpropylbenzenesulfonam e zenesulfonamide 2,5-Dipropyl-4-trifluoromethylben- 4-Cyano-2-ethyl-5-isopropylbenzenesulfonamide 4-Cyano-2,5-diisopropylben-. zenesulfonamide 5-Cyano-2,4-diisopropylbenzenesulfonamide 3-Cyano-2,5 -diisopropylbenzenesulfonamide 3-Bromo-4-cyano-2,5- diisopropylbenzenesulfonamide 3-Chloro-4-cyano-2,5- d iisopropylbenzenesulfonamide 2-Ethyl-5-isopropyl-4- trifluoromethylbenzenesulfonamide N,N-Diallyl-2,5-diisopropyl-4- trifluoromethylbenzenesulfonamide 2,4-Diisopropyl-S-trifluowmethyl- I benzenesulfonamide 1 2,5-Diisopropyl 34rifluoromethylbenzenesulfonamide '3-Bromo-2,5-diisopropyl-4- trifluoromethylbenzenesulfonamide 3-Chloro-2,5-diisopropyl-4- trifluoromethylbenzenesulfonamide EXAMPLE l1 1 Methyl N-(4-Cyano-2,5-diisopropylphenylsulfonyl)- formimidate To a mechanically stirred mixture of 27 parts of 4- cyano-2,5-diisopropylbenzenesulfonamide and l 22 'partstrimethyl orthoformate was. added a trace of p-toluenesulfonic acid. The reaction was heated at reflux for 4 hours. It was filtered, the filtrate stripped to dryness in vacuo, and the resulting solid recrystallized from methanol to give the title product, .m.p. 130 132.

The following formimidic or acetimidic acid esters are prepared from the listed benzenesulfonamides and an ester selected from trimethyl or triethyl orthofor mate or trimethyl or triethyl orthoacetate by the procedure of the above example. I

TABLE 10- Continued Starting Material Product 4-cyanomethyl-2,S-diisopropylbenzenesul- N-acetyl-4-cyanomethyl-2,S-diisopropylbenzenefonamide sulfonamide 2,5-diisopropyl-4-nitrobenzenesulfonamide N-acetyl2,5-diisopropyl-4-nitrobenzenesulfonamide 2,5-diisopropyl-4-trifluoromethylbenzene- N-acetyl-2,5-diisopropyl-4-trifluoromethylbensulfonamide zenesulfonamide EXAMPLE l3 Compositions The compounds of Formula (1) can be formulated .for herbicidal use in conventional ways. The formulations can be wettable or water-soluble powders, dusts, suspensions in water and/or organic solvents, solutions, emulsifiers, high-strength compositions, pellets or granules. Other herbicides can be tank-mixed with the compounds of Formula (1) in the form of finished formulations or they can be combined to give single formulations for reasons of convenience. The formulations will include inert carrier materials and/or surfactants which serve as wetting, emulsifying and/or dispersing agents. Anionic or nonionic surfactants are preferred; lists of suitable surfactants can be found in Detergents and TABLE 11 Starting Material Product 4-cyano-2,5-diisopropylbenzenesulfonamide sodium 4-cyano-2,S-diisopropylbenzenesulfonamide, m.p. 295-300 4-cyano-2,5-diisopropylbenzenesulfonamide amide 4-cyano-2,5-diisopropylbenzenesulfonamide amide 4-chloro-2,5-diisopropylbenzenesulfonamide lithium 4-cyano-2,5-diisopropylbenzenesulfoncalcium 4-cyano-2,S-diisopropylbenzenesulfonpotassium 4-chlore-2,5-diisopropylbenzenesulfonamide, m.p. 300

4-chloro-2,5 -diisopropylbenzenesulfonamide m.p. 275 4-chloro'2,5 -diisopropylbenzenesulfonamide amide 4-chlore-2,5-diisopropylbenzenesulfonamide amide 4-bromo-2,S-diisopropylbenzenesulfonamide m.p. 250 4-bromo-2,5-diisopropylbenzenesulfonamide amide 4-cyan0-5-isobutyl-2-isopropylbenzenesulfonamide fonamide 4-cyano-5-isobutyl-2-isopropylbenzenesulfonamide sulfonamide 4-chloro-5 -isobutyl-2-isopropylbenzenesulfonamide 4-chloro-S-isobutyl-2-isopropylbenzenesulfonamide sulfonamide 2-secbutyl-4-cyano-5-is0pr0pylben2enesulfonamide fonamide 2-sec-butyl-4-cyano-5-isopropylbenzenesulfonamide I sulfonamide 2-sec-butyl-4-chloro-5-isopropylbenzenesulfonamide fonamide 2-sec-butyl-4-chloro-5-isopropylbenzenesulfonamide sulfonamide 4-cyano-2,5-di-sec-butylbenzenesulfonamide amide 4-chloro-2,5-di-sec-butylbenzenesulfonamide amide 5-chloro-2,4-diisopropylbenzenesulfonamide amide 5-cyano-2,4-diisopropylbenzenesulfonamide amide 4-cyanomethyl-2,5-diisopropylbenzenesulfonamide 2,5-diisopropyl-4-nitrobenzenesulfonamide fonamide mide 2,5-diisopropyl-4-nitrobenzenesulfonamide fonamide 2,5-diisopropyl4-trifl uoromethylbenzenesulfonamide potassium 2,5-diiso sodium 4-chloro-2,5-diisopropylbenzenesulfonamide,

lithium 4-chlore-2,5-diisopropylbenzenesulfoncalcium 4-chloro-2,5-diisopropylbenzenesulfonsodium 4-brom0-2,S-diisopropylbenzenesulfonamide,

potassium 4-bromo-2,5-diisopropylbenzenesulfonsodium 4-cyano-5-isobutyl2-isopropylbenzenesulpotassium 4-cyano-S-isobutyl-2-isopropylbenzenesodium4-chloro-5-isobutyl-2-isopropylbenzenesulpotassium 4-chloro-5-isobutyl-2-isopropylbenzenesodium 2-sec-butyl-4-cyano-5-isopropylbenzenesulpotassium 2-sec-butyl-4cyano-5-isopropylbenzenesodium 2-sec-butyl-4-chloro-5-isopropylbenzenesulpotassium 2-sec-butyl-4-chloro-S-isopropylbenzenepotassium 4-cyano-2,S-di-sec-butylbenzenesulfonsodium 4-chloro-2,5-di-sec-butylbenzenesulfonpotassium 5-chloro-2,4-diisopropylbenzenesulfonsodiurn 5-cyano-2,4-diisopropylbenzenesulfonsodium 4-cyanomethyl-2,5-diisopropylbenzenesulsodium 2,5-diisopropyl-4-nitrobenzenesulfonapropyl-4-nitrobenzenesulsodium 2,5-diisopropyl-4-trlfluoromethylbenzenesulfonamide Emulsifiers Annual (1971) by John W. McCutcheon, Inc. The formulations will contain about 2 to 99% by weight, of active compound or compounds, up to about 20% by weight of a surfactant, and/or up to about 98% by weight or inert solid or liquid carrier. For dusts or granules, 1 to 25% of active compound can be used, for pellets 550%, for solutions or suspensions 550%, for wetting powers -90%, for water-soluble powder 20- 95% and high-strength compositions 90-99%. In some instances the surfactant may be used at up to 5 times the amount of active which may improve the effectiveness of the active compound. This amount of surfactant is most conveniently applied as a tank-mix with the active component.

Organic liquids suitable for preparation of solutions, suspensions, and emulsifiable concentrates containing the compounds of Formula (1) include alcohols, glycols, monoand dialkyl ethers of ethylene glycol and diethylene glycol, ketones, esters, sulfamides, amides, tetrahydrofuran, paraffinic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons. Choice of a liquid is dictated by the reactivity, the solubility of the active compound to be used and whether a suspension or solution is desired. Compounds of Formula (1) can be formulated as aqueous suspensions or solutions depending upon whether the sulfonamides or their salts are used.

Solid, inert carrier materials suitable for wettable powders, pellets and granules include natural clays, synthetic fine silicas, and other materials commonly used for this purpose.

Further information concerning the preparation of herbicidal formulations can be found in US. Pat. No. 3,235,357.

Some preferred herbicidal compositions and methods of this invention are illustrated by the following examples, wherein all parts, proportions, and percentages are by weight unless indicated otherwise.

The above ingredients are blended, hammer-milled to pass a 0.25 mm screen, air-milled in a fluid-energy mill, and reblended.

The following compounds can be formulated in like manner. Ethyl-N-(4-cyano-2,5-diisopropylphenylsulfonyl)-formimidate, 3-chloro-2,5-diisopropyl-4- trifluoromethylbenzenesulfonamide and 2,5-diisobutyl- 3-nitrobenzenesulfonamide.

One kilogram of the above formulation and one kilogram of 50% wettable linuron are suspended in 200 liters of water and applied preemergence to a hectare of soybeans planted in Butlertown silt loam soil. Compared with the results obtained on a control plot on which no herbicide is used, this treatment controls all weeds present without injury to the crop and it produces an excellent yield.

EXAMPLE C 4-cyano-2,5-diisopropylbenzenesulfonamide 25% polyoxyethylene sorbitol hexaoleate 5% highly aliphatic hydrocarbon oil The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting rather thick suspension may be applied directly, extended with oils, or emulsitied in water.

Four kilograms of the above formulation are emulsified in 200 liters of water and applied preemergence to a hectare of soybeans planted in Norfolk sandy loam soil. The treatment controls a number of weeds, particularly weedy grasses, and the soybeans, grown without competition produce an excellent yield.

EXAMPLE D 4-cyano-2,5-diisopropyl-N,N-dimethylbenzenesulfonamide 4% attapulgite granules (15-30 mesh, 0.59

app. 1.25 mm) 90% dimethylformamide 6% A 40% solution of the active ingredient in dimethylformamide is prepared by warming the two materials with stirring. This solution is then sprayed on the granules which are tumbled in a blender. The granules so prepared are suitable for application without removal of solvent.

Fifty kilograms of these granules are distributed preemergence over a hectare of cotton planted in silt loam soil. One kilogram of diuron wettable powder is applied as a spray in water at the same time the granules are distributed. This treatment controls a wide variety of weeds without injury to the cotton, which grows and produces an excellent yield of high-quality lint.

The above ingredients are ground to pass a 0.3 mm screen, blended, moistened with water, extruded and cut into pellets. After drying, these pellets can be applied directly or they can be further subdivided into 30-60 mesh (0.25-0.59 mm) granules for more uniform application. All compounds of this invention can be formulated in like manner.

Twenty kilograms of the above granules are distributed behind the planter to a hectare of soybeans being planted in silt loam soil containing 3% organic matter. The treatment controls all weeds present, both broadleaves and grasses, without damage to the crop, which 5 4-chloro-2,5-dllsopropylbenzene grows without weed competition and produces an exlf id 6% cellent yield. Ordram" 63 (molinate)* 4% attapulgite granules (24-48 mesh) 75% EXAMPLE F dimethylformamide 15% 10 *S-cthyl hexahydro-l-Hazepine-l-carbothioate 4-cyano-2,S-diisopropylbenzenesulfonamide 987 trimethylnonyl polyethylene glycol a The active ingredients are dissolved in the d1methylether 2% formamide with warming, and the solution is sprayed on the granules which are tumbled in a mixer. The The above ingredients are blended, hammer-milled granules are then screened to remove fines and packto pass a 0.25 mm screen and reblended. This composiaged. tion can be used directly or as a source of active for Ten kilograms of the above granules are spread uniother formulations. formly on a hectare of rice paddy soon after the'rice is One kilogram of the above formulation and one kilotransplanted. Numerous grass and broadleaf weeds are gram of fluometuron are tank-mixed in 400 liters of controlled without injury to the rice which provides exwater and sprayed preemergence on a hectare of cotceptional yields due to growth unencumbered by comton planted in Commerce silt loam soil. The cotton petlng weeds. emerges to a good stand and grows vigorously without competition from crabgrass, sprangletop (Leptochloa EXAMPLE J spp.) barnyard grass, pigweed, seedling .lohnsongrass, goosegrass, ragweed, spotted spurge (Euphorbia 4 cyano z,idiisowowlbenzeng maculata L. or other weeds controlled by the treat- 3 sulfonamidfi I l d h 1 egg, -(p-cumeny imet yurea 0 ment. To obtain similar results, tank mixes are made of Sodium alkylnaphthalenesulfonate 2% the above formulation with one of several other herbls i m N-methyI-N-oleoyltaurate 3% cides including diuron at 0.8 kilogram, monuron at 1 dlammacecus earth 20% kilogram, prometryne at 2 kilograms, norea at 2 kilograms and chloropropham at 4 kilograms per hectare. The above ingredients are blended and hammer milled to particles nearly all below 50 microns and re- Two kilograms of the above wettable powder are dis- 4-bromo-2,5-diisopropyl-N,N-dimethyl- I persed with mechanical agitation in 400 liters of water benzenesulfonam'de 20% and sprayed preemergence on a hectare of cotton octylphenyl polyethylene glycol ether 2% dimethylformamide 78% planted in Crowley silt loam SOll. Many weeds are con- I 40. trolled while the cotton grows vigorously to maturity The above ingredients are stirred together to produce glvmg an excellent yleld of v v a solution suitable for low-volume application.

Two liters per acre of the above formulation is di- EXAMPLE K luted with dimethyl formamide to 10 liters and applied by airplane to recently planted, but not yet emerged, 4yano.2,5 diisopr9py| N,N dimethyl.l spring wheat to control downy bromegrass and other benzenesulfonallllde 4-chloro-4-ethylammo-6-1sopropylannual grasses Wl'llCh reduce wheat yields if allowed to amino s triazine (a twine) 25% compete with the wheat. attapulgite clay 22 sodium llgmn sulfonate 2% EXAMPLE H 50 dioctyl sodium sulfosuccinate 1% Aqueous Suspension The above ingredients are blended, hammer-milled v sulfonamide 30% to particles nearly all below 50 microns and reblended.- l 2% Four kilograms of the above formulation are discalclum llgmn sulfonate 15% sodium carbonate 2% persed m 450 liters of water and sprayed uniformly on I sodium pentachlorophenate 8;? a hectare of sugarcane before the weeds and the crop water have emerged. The sprayed area remains free of weeds including crabgrass, goosegrass, seedling .lohnsongrass, All the above mgl'edlems except the water are foxtail, pigweed and ragweed. The sugarcane grows blended and ground to pass a 20-mesh screen. The igorously and produced a high yield. water is then added, and the mixture is sand-ground EXAMPLE L until the solid particles are smaller than 10 microns.

Three kilograms of the above formulation aremixed 1 44, .2, a" l-N,N- th I in 450 liters of water with mechanical agitation and z 'zg i i ggggg Y 3 sprayed preemergence on a hectare of soybeans 3-(3,4-dichlol'ophenyl)-l,l-dimethyl- 30% urea planted in Galllon fine sandy loam. The soybeans sodium akylnaphthalenesulfonate 2% emerge to a good stand and grow vigorously to maturity odium N-dmethyl-tlltll-oleoyltaurate 3% finely divi ed syn etic silica 2% unencumbered by weeds such as barnyard grass, pig diawmaceous earth v 33% weed, foxtail, crabgrass and fall panicum (Panicum dichotomiflorum) which are controlled by the treatment.

EXAMPLE I The above ingredients are blended, hammer-milled to pass a 50-mesh screen and reblended.

The formulation of this example is applied to a railroad right-of-way heavily infested with weeds. The use rate is 30 kilogram of formulation per hectare of area treated. The weeds on the test area are quickly killed and reinfestationis prevented for a period of one year.

EXAMPLE M 4-cyano-2,5-diisopropylbenzenesulfonamide 25% 5-bromo-3-sec-butyl-6-methyluracil (bromacil) 25% sodium N-methyl-N-oleoyltaurate 3% sodium alkylnaphthalenesulfonate 2% diatomaceous earth 45% The above ingredients are blended, hammer-milled to particles nearly all below 50 microns and reblended.

The following compounds can take the place of the 4-cyano-2,5-diisopropylbenzenesulfonamide: t

methyl N-(4-cyano-2,5-diisopropylphenylsulfonyl)formimidate N-acetyl-4-cyano-2,5-diisopropylbenzenesulfonamide 2,5-diisopropyl- 4-trifluoromethylbenzenesulfonamide 3-nitro-2,5-dipropylbenzenesulfonamide Forty kilograms of the above formulation are applied to a hectare of land in a tank farm area. An existing population of weeds is quickly killed and the area kept free of plant growth for a period of many months.

EXAMPLE N 4-chloro-2,5-diisopropylbenzenesulfonamide 15% 3-( p-cumenyl)- l l -dimethylurea 15% paraffinic hydrocarbon oil 61% polyoxyethylene sorbitol heptaoleate 8% synthetic fine silica 1% produce particles essentially all below 5 microns. For

' application, the product can be extended with either oils or water. An emulsion is formed in the latter.

Four liters of the above formulation are added to a 2000 liter spray tank filled with water and provided with continuous bypass agitation. The emulsion is sprayed on a hectare of direct seeded rice. The treatment controls barnyardgrass, junglerice and many other weeds in the field. The rice grows well without weed competition and produces a good yield.

EXAMPLE sodium i-cyano-LS-diisopropylbenzenesulfonamide 95.0% sodium lauryl sulfate 0.5% finely divided synthetic silica 4.5%

The above ingredients are blended, ground to pass an 0.42 mm screen and reblended to form a water-soluble powder. The following compounds can be formulated in like manner: potassium 4-cyano-2,5-diisopropylbenzenesulfonamide sodium 4-chloro-2,5-diisopropylbenzenesulfonamide potassium 4-chloro-2,5-diisopropylben'zenesulfonainide One kilogram of the above formulation is dissolved in 400 liters of water and sprayed preemergence to an The ingredients are combined and sand-milled to acre of cotton planted ona Boskett slit loam soil'with 2% organic matter. Weeds infesting the area consisting primarily of crabgrass, brachiaria, sprangletop, barnyardgrass, pigweed and ragweed, are controlled. The cotton grows vigorously to maturity.

EXAMPLE P lithium 4-cyano-2,S-diisopropylbenzenesulfonamide 24.0% ethylene glycol 50.0% methanol 4.0% ethanol 5.0% water 17.0%

EXAMPLE Q 4-chloro-2,S-diisopropylbenzenesulfonamide 22.0% lithium hydroxide monohydrate 4.0% ethylene glycol 35.0% methanol 4.0% water 35.0%

The above ingredients are blended with warming to produce a water-soluble liquid concentrate.

One part of the above liquid concentrate is dissolved .in 9 parts of water and sprayed preemergence by airplane at a volume rate of 30 liters per hectare on rice drill planted in a Crowley silt loam soil. Barnyardgrass, spangletop and dayflowers are controlled, allowing the rice to grow unencumbered by serious weed competition, thereby producing a good yield of grain.

EXAMPLE R methyl N-(4-cyano-2,5-diisopropylphenylsulfonyl)formimidate 20.0% xylene 25.0% isophorone 51.0% blend of oil-soluble sulfonates and polyethoxyethylene ethers 4.0%

The above ingredients are blended with warming to form an emulsifiable concentrate. The following compounds can be formulated in like manner: ethyl N-(4-cyano-2,5-diisopropylphenylsulfonyl)formimidate 4-cyano-N-( l-ethoxyethylidene)-2,5-diisopropylbenzenesulfonamide methyl N-( 4-chloro2,5-diisopropylphenylsulfonyl)formimidate ethyl N-(4-chloro 2,5-diisopropylphenylsulfonyl)formimidate This formulation is emulsified with water in a volume ratio of l to 7 and sprayed prremergence by airplane at the rate of 20 liters of spray per hectare 0n Riverdale clay loam recently planted to spring wheat. Wild oats and cheatgrass are controlled and the wheat matures to produce a good yield.

In the following composition claims, the term con- I sisting essentially of means that in addition to the re cited components the composition also may contain other components which do not adversely affect its effectiveness for the intended use.

I claim:

1. A compound of the formula e. the total carbon content of R R R and R is not greater than 9 carbon atoms; and

f. each alkyl group has from 2 to 3 carbon atoms in a straight chain from the point of attachment to the aromatic ring; and

R is hydrogen, alkyl of l to 3 carbon atoms, allyl or p py y R is hydrogen, alkyl of l to 3 carbon atoms, allyl, propynyl, lithium, sodium, potassium, calcium or acyl or 1 to 3 carbon atoms; and R and R together can form where misOorlandnisOor l. 2. A compound of claim 1 wherein Z is cyano; R R and R are hydrogen; R is hydrogen, lithium, potassium or sodium; R is alkyl of 3 to 5 carbon atoms, and R is alkyl of 3 to 5 carbon atoms. 3. the compound of claim 1, 4-cyano-2,5-diisopropylbenzenesulfonamide. 

1. A COMPOUND OF THE FORMULA
 2. A compound of claim 1 wherein Z is cyano; R2, R4, and R5 are hydrogen; R6 is hydrogen, lithium, potassium or sodium; R1 is alkyl of 3 to 5 carbon atoms, and R3 is alkyl of 3 to 5 carbon atoms.
 3. the compound of claim 1, 4-cyano-2,5-diisopropylbenzenesulfonamide. 